meso-Aryl-substituted [26]hexaphyrin(1.1.0.1.1.0) and [38]nonaphyrin(1.1.0.1.1.0.1.1.0) from oxidative coupling of a tripyrrane.
meso-Aryl-substituted [26]hexaphyrin(1.1.0.1.1.0) and [38]nonaphyrin(1.1.0.1.1.0.1.1.0) from oxidative coupling of a tripyrrane.
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DOI：
10.1002/anie.200463054
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发表时间：
2005-04
影响因子：
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通讯作者：
Soji Shimizu;R. Taniguchi;A. Osuka
中科院分区：
文献类型：
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作者：
Soji Shimizu;R. Taniguchi;A. Osuka
近年来，由于其独特的光学、电化学和配位性质，以及作为阴离子或中性底物受体的潜在用途，膨胀卟啉的开发出现了激增。[1]Rubyrin，代表一类[26]六卟啉（1.1. 0.1. 1.0)大环化合物，首先由Sessler等人合成并表征为β-十二碳-（烷基）-取代的分子的双阳离子。[2，3]一系列带有meso-aryl取代基的核修饰的红比林也已经被Erashekar及其同事探索。[4]迄今为止所制备的红宝石都具有强的环电流，与其26-π-芳香环相一致。此外，双阳离子红比林已被证明是阴离子的良好受体，[2，4]但除了母体红比林的情况外，对所得络合物的结构细节的研究很少。本文报道了meso-芳基取代的红比啉2的合成及其阴离子识别行为。据我们所知，一个全氮杂异构体的meso-芳基取代的红比林还没有报道，尽管它的重要性，扩大卟啉的化学。除了红比林衍生物，其高级同系物九卟啉（1.1。0.1. 1.0. 1.1. 0)并对其结构进行了表征。按照Errashekar及其同事[4 b，c]报道的方法，将内消旋-五氟苯基取代的三吡咯烷1 [5]在CH 2Cl 2中的溶液在室温下用0.5当量的三氟乙酸（TFA）在CH 2Cl 2中处理90分钟，然后加入3当量的四氯苯醌（四氯-1，4-苯醌），随后将混合物加热回流90分钟。通过柱色谱法进行连续分离，得到红比林5，10，19，24-四（五氟苯基）-[26]己卟啉-（1.1. 0.1. 1.0）（2）为稳定的紫色固体，产率24%，以及5，10，19，24，33，38-六（五氟苯基）-[38]九卟啉
In recent years, there has been a surge in the development of expanded porphyrins which has been boosted by their unique optical, electrochemical, and coordination properties, as well as their potential uses as receptors of anionic or neutral substrates.[1] Rubyrin, which represents a class of [26] hexaphyrin (1.1. 0.1. 1.0) macrocycles, was first synthesized and characterized by Sessler et al. as a dication of a β-dodeca-(alkyl)-substituted molecule.[2, 3] A range of core-modified rubyrins that bear meso-aryl substituents have also been explored by Chandrashekar and co-workers.[4] The rubyrins prepared so far all exhibit a strong diatropic ring current in line with their 26-π-aromatic circuit. Furthermore, dicationic rubyrins have been shown to serve as a good receptor for anions,[2, 4] but structural details of resultant complexes have been only poorly studied except for the case of the parent rubyrin. Herein we report the concise synthesis of meso-arylsubstituted rubyrin 2 and interesting anion-recognition behavior of its dication. To the best of our knowledge, an all-aza isomer of a meso-aryl-substituted rubyrin has not been reported, despite its importance in the chemistry of expanded porphyrins. Besides the rubyrin derivative, its higher homologue nonaphyrin (1.1. 0.1. 1.0. 1.1. 0) was also obtained, and its structural characterization is also described here. Following the method reported by Chandrashekar and coworkers,[4b, c] a solution of meso-pentafluorophenyl-substituted tripyrrane 1 [5] in CH2Cl2 was treated with 0.5 equivalents of trifluoroacetic acid (TFA) in CH2Cl2 for 90 minutes at room temperature, then 3 equivalents of chloranil (tetrachloro-1, 4-benzoquinone) was added, and the mixture was subsequently heated at reflux for 90minutes. Sequential separations by column chromatography provided the rubyrin 5, 10, 19, 24-tetrakis (pentafluorophenyl)-[26] hexaphyrin-(1.1. 0.1. 1.0)(2) as a stable violet solid in 24% yield, and 5, 10, 19, 24, 33, 38-hexakis (pentafluorophenyl)-[38] nonaphyrin